Organochlorine pesticides and PCB residues in sediments of Alexandria Harbour,Egypt

Persistent organochlorine compound concentrations were determined for 23 surface sediment samples collected from Alexandria Harbor, Egypt. Total PCB concentrations ranged from 0.9 to 1210 ng/g with four to seven Cl-substituted biphenyls being the most prevalent PCBs congeners. Different PCB congener distribution patterns were observed, probably reflecting different inputs and attenuation at various locations. Total DDT concentrations varied from <0.25 ng/g to 885 ng/g. The ratios of DDTs (2,4^′- and 4,4^′-DDT)/total DDTs (DDTs plus metabolites) in sediment samples from certain sites were 0.86 or higher, indicating little attenuation or recent input of DDT. Total chlordane (the sum of heptachlor and its epoxide, oxy-, γ- and -chlordane and cis+trans-nonachlor) ranged from <0.25 to 44 ng/g with the highest concentration found in the Arsenal Basin. The geographic distributions of PCBs, total DDTs and total chlordane were similar. Chlorinated benzenes (CBs), hexachlorocyclohexanes (HCHs), aldrin, dieldrin, endrin, chloropyrifos, endosulfan, mirex and pentachloroanisole were below detection limits or detected at low concentrations in most of the samples. Sites that were contaminated with high concentrations of organochlorine compounds were associated with dense population and low energy environment. The contamination levels of PCBs, total DDTs and total chlordane were in high range compared to other locations worldwide.     

Composition and distribution of organochlorine pesticide residues in surface sediments from the Wu-Shi River Estuary,Taiwan

The contamination of organochlorine pesticides (OCPs) in sediments from the Wu-Shi River estuary was investigated to evaluate the pollution potentials and distribution of OCPs in central Taiwan. A total of 19 sediment samples were collected at five sampling stations along the River estuary. The concentrations of OCPs were in the range of 0.99–14.5 ng/g-dry weight (dw) for ΣHCH (-, β-, γ-, δ-HCH), 0.46–13.4 ng/g-dw for Σcyclodiene and 0.53–11.4 ng/g-dw for ΣDDT (p,p^′-DDD, p,p^′-DDE, p,p^′-DDT). The mean concentrations of ΣHCH, Σcyclodiene and ΣDDT were 3.79, 4.87 and 2.51 ng/g-dw, respectively. The total concentrations of OCPs correspond to 1.73–71.9 μg/g-OC when normalized to TOC contents. Among the organochlorine pesticides, endosulfan sulfate, β-HCH, and p,p^′-DDD were the most dominant compounds in the sediments with the average concentrations of 1.97, 3.43 and 2.08 ng/g, respectively. Also, different contamination patterns among sampling seasons were observed. The measured concentrations of OCPs collected in spring were higher than those in autumn and winter. A linear relationship between sediment characteristics and OCP residues was also demonstrated. The results obtained in this study show that there still exist a variety of organochlorine pesticide residues in the sediments from the near shore of central Taiwan.     

Organochlorine pesticide residues in sediments and biota from the coastal area of Dar es Salaam city,Tanzania

Sediment and biota samples were collected from Msimbazi and Kizinga rivers and from the coastal marine environment of Dar es Salaam during both dry and wet seasons. The samples were analyzed for various organochlorine pesticide residues using GC-ECD and GC-MS. Dieldrin, p,p^′-DDT, p,p^′-DDE, p,p^′-DDD, o,p^′-DDT and γ-HCH were detected at significantly greater concentrations above the method detection limits. Recoveries of pesticide residues ranged 86.5–120% in sediments and 62–102% in biota. The average concentrations of total DDT in sediments for the two seasons were almost the same. Biota samples showed significant difference in levels of residues depending on mode of feeding and age of analyzed biota. p,p^′-DDT to total DDT ratios in all matrices indicated recent use of DDT. The levels of residues in sediments suggest possible adverse effects to humans consuming biota that are directly exposed to the sediments. This effect, which is associated with bio-concentration of residues in the tissues of edible aquatic biota, should not affect wildlife. In spite of concern on the adverse effect to humans posed by pesticide residues in sediments, edible biota from the examined water bodies were found to be safe for human consumption.     

Field accumulative behavior of organochlorine pesticides. The role of crabs and sediment characteristics in coastal environments

The influence of intertidal crab beds on the concentrations of organochlorine (OC) pesticides in sediment was studied in two different coastal environments in Argentina. Samples of male burrowing crabs (Chasmagnathus granulatus) were collected for this study. Our field data showed lower bioaccumulation of OC pesticides in crabs from sediments with a higher total organic carbon (TOC) and higher clay content. Thus, concentrations in crabs depend on the physico-chemical characteristics of the sediment where they live more than on the OC pesticide concentrations in the environment. The distribution patterns in sediment from inside and outside crab burrows were similar for both coastal areas being HCHs  γ-chlordane > p,p′-DDE for San Antonio Bay (SAO), and HCHs > p,p′-DDE  γ-chlordane for Mar Chiquita (MCh) coastal lagoon. OC pesticide concentrations in sediment were significantly lower inside than outside crab burrows, irrespective of the sediment physico-chemical characteristics due to the bioturbation activity of C. granulatus.     

PCBs and chlorinated pesticides in the atmosphere and aquatic organisms of Ross Island, Antarctica

PCBs, p,p′-DDT, p,p′-DDE and lindane (γ-hexachlorocyclohexane) were monitored in the lower atmosphere of Ross Island, in Antarctica for 2 yr. Geometrical means were 15.2 pg m⁻³ for PCBs, 2.0 pg m⁻³ for p,p′-DDT, 1.0 pg m⁻³ for p,p′-DDE and 25.8 pg m⁻³ for lindane. Atmospheric levels of lindane were positively correlated with temperature, and a significant difference was found between spring-summer and summer-winter concentrations. No season related differences were found for the other chlorinated hydrocarbons, possibly owing to their lower vapour pressure and the cold climate. Periods with increased atmospheric levels of PCBs and DDT compounds were recorded. Lindane, p,p′-DDE and PCBs were present in fish and zooplankton sampled close to Ross Island. Pollutant levels in the zooplankton (on an extractable fat basis) were highest during the Antarctic spring and autumn and were inversely correlated to their fat content.     

Levels of organochlorine pesticide residues in some organs of the Ganges perch, Lates calcarifer, from the Ganges-Brahmaputra-Meghna Estuary, Bangladesh

Levels of organochlorine pesticide residues (p,p′ DDT, DDD, DDE, Aldrin, Dieldrin, Lindane, Heptachlor and BHC) were analysed in the dry and wet seasons in four organs (muscle, liver, gut and egg samples) of Ganges Perch, Lates calcarifer, collected during October–November–December, 1996 and May–June–July, 1997 from the Ganges–Brahmaputtra–Meghna estuary. The residues were analysed by using gas-chromatography (GC) in electron capture detector (ECD) mode and were verified by thin layer chromatography (TLC). Among the four organs analysed, the residues were found in the order egg > gut > muscle > liver. The pesticide residues were found in the order ∑DDT > Heptachlor >Dieldrin > Aldrin. Higher levels of residues were found during the dry season due to high lipid content in fishes. A positive correlation was observed between the pesticide residues (∑DDT and ∑OCs) and lipid contents of fish, and the correlation was found to be linear. The concentrations of pesticide residues in muscle, liver and gut were below the FAO/WHO (1993) recommended permissible limit except in eggs.     

Mercury concentrations in stomach contents and muscle of five fish species from the north east coast of England

Mercury concentrations in stomach contents and muscle tissue are reported for five fish species: herring (Clupea harengus), whiting (Merlangius merlangus), roker (Raja clavata), plaice (Pleuronectes platessa) and dab (Limanda limanda) collected in summer 1992 off the mouth of the River Tyne, North East England. Median muscle mercury concentrations in the area increase in the order plaice < herring < roker < dab < whiting. Absolute mercury concentrations and muscle mercury-length relationships indicate that the environmental availability of mercury in the study area is low. Stomach contents were recovered from dab, plaice and roker only. Median mercury concentrations in stomach contents increased in the order plaice < roker < dab. The variability of the ratio (muscle mercury/stomach content mercury) has been examined for these three species. In dab the variation is relatively low (39.7% RSD), whereas in plaice and roker it is considerably higher (128.4% and 184.6%, respectively). If stomach content mercury concentrations accurately reflect local mercury availability then dab muscle tissue would make a more reliable availability index than muscle tissue of plaice or roker.     

Contamination by Persistent Organochlorines in Small Cetaceans from Hong Kong Coastal Waters

Blubber samples of 2 cetacean species, the Indo-Pacific hump-backed dolphin (Sousa chinensis) (n=11) and finless porpoise (Neophocaena phocaenoides) (n=9), collected from Hong Kong coastal waters were analysed for persistent organochlorines. Mean concentration in the blubber of DDTs was ranked first (46 μg/g wet wt.), followed by PCBs (24 μg/g wet wt.), HCHs (0.76 μg/g wet wt.), chlordane compounds (0.38 μg/g wet wt.) and HCB (0.07 μg/g wet wt.). The present cetacean species may potentially be faced with high risk due to the elevated level of DDTs and PCBs. Relatively high concentrations of PCBs and DDTs can be attributed to the continuous environmental input of these compounds in the Far East region including Hong Kong. Highly chlorinated PCBs such as IUPAC Nos. 138, 153, 180 were the prominent congeners, accounting for 39% of the total PCBs. Mean concentrations of 6 non- and mono-ortho coplanar congeners were 2.1 and 2.8 μg/g wet wt. in the hump-backed dolphin and finless porpoise, respectively. Among highly toxic coplanar PCBs, mono-ortho congener IUPAC No. 118 and non-ortho congener IUPAC No. 126 were estimated to have the greatest toxicity contribution. Tris(4-chlorophenyl) methane (TCPMe) and tris(4-chlorophenyl) methanol (TCPMeOH), which have been the most recently identified microcontaminants, were also detected with the highest concentration of 290 and 300 ng/g (wet wt. basis), respectively. The concentrations of TCPMe relative to TCPMeOH in cetaceans from Hong Kong coastal waters were significantly higher than those found in various seals collected from other parts of the world, suggesting the different metabolic system of these two compounds between seals and cetaceans. Correlations between the concentrations of tris-chlorophenyl compounds with other persistent organochlorines such as HCHs, CHLs, DDTs and PCBs were significant, suggesting their accumulation nature similar to these organochlorines.     

Profiles of Fecal Porphyrins in River Otters Following the Exxon Valdez Oil Spill

Median levels of Coproporphyrin III (Copro III) in fecal samples of river otters (Lontra canadensis) collected from an oiled area in Prince William Sound, Alaska, USA, during 1990 were significantly higher than in samples collected from the same oiled area during 1996 (p=0.011, one way analysis of variance), a nonoiled reference area in Prince William Sound during 1996 (p=0.002) and a reference area in southeast Alaska during 1998 (p=0.004). An overall test of significance that combined probabilities from the statistical analysis of this porphyrin study with those from other biomarker studies revealed a significant difference in physiological response of river otters between oiled and nonoiled areas of the Sound for 1990 (p < 0.01). We demonstrated that changes in levels of fecal porphyrins may serve as a biomarker that may contribute to a health assessment of wild river otters.     

Persistent organochlorine residues and toxic evaluation of polychlorinated biphenyls in sharks from the Mediterranean Sea (Italy)

Persistent organochlorines such as polychlorinated biphenyls including coplanar congeners, DDT compounds and HCB were measured in different tissues (muscle, liver and eggs) of two Mediterranean shark species: namely Centrophorus granulosus and Squalus blainvillei. The concentrations of organochlorines in the tissues and organs of both species were in the order DDTs>PCBs>HCB. The highest values of DDTs, PCBs and HCB were found in liver followed by eggs and muscle. Among DDTs the compound found in greatest concentration was p,p^′-DDE. The PCB profiles were dominated by congeners 138, 153, and 180. The isomers with higher TEQs values were non- and mono-ortho congeners than di-ortho ones in muscle, liver and eggs of both species. Among the non-ortho, PCB 126 was the major contributing individual to the total TEQs in both species.     

Assessment of PAH Pollution in Coastal Areas from the NW Mediterranean through the Analysis of Fish Bile

Polycyclic Aromatic Hydrocarbon (PAH) pollution in coastal areas from the NW Mediterranean has been assessed by measuring bile PAH metabolites in two fish species, the red mullet – Mullus barbatus-and the sea comber – Serranus cabrilla – Bile crude samples were directly analysed by LC-fluorescence at the excitation/emission wavelengths of benzo[a]pyrene (380/430 nm). Subsequently, bile samples were hydrolysed and analysed by (a) LC-fluorescence at the excitation/emission wavelength pairs of naphthol (290/335 nm) and pyrenol (345/395 nm), and (b) gas chromatography–mass spectrometry (GC–MS) for the determination of individual PAHs. Qualitative and quantitative differences were recorded among sampling sites. Both species allowed us to detect different pollution gradients, the highest levels of FACs were observed in organisms caught in the vicinity of big industrial cities, whereas the lowest levels were recorded in organisms from Corsica and Sardinia. The obtained results highlight the usefulness of the LC-fluorescence technique as an initial screening method to assess PAH exposure in coastal fish.     

Esterase activities and lipid peroxidation levels in offshore commercial species of the NW Mediterranean Sea

There is a lack of information on monitoring neurotoxicity in offshore commercial species. To help fill this gap, we sampled hake (Merluccius merluccius) and Norway lobster (Nephrops norvegicus) in fishing grounds off the coast of l’Ametlla de Mar (NW Mediterranean) in June 2005 at a depth of 100 m and 400 m. Additionally, at 400 m depth, two other fish species, Micromesistius poutassou and Phycis blennoides were included. Neurotoxicity markers such as Colinesterases (ChEs), namely acethyl- (AChE), butyryl- (BChE), propionyl- (PrChE) and carboxilesterase (CbE) were measured in muscle. Lipid peroxidation (LP), a marker of oxidative damage, was also included. The results are discussed in relation to the animal’s sex, size and fishing depth. A comparison of esterases and LP levels between muscle and liver of hake and between muscle and hepatopancreas of Norway Lobster was made.

AChE was dominant in muscle and CbE in hepatopancreas. No differences between fish species were seen for AChE. However, N. norvegicus, presented lower levels of ChEs and LP. A size-dependence in ChEs was seen for M. merluccius, with larger animals showing significantly lower activities (p < 0.05). Sex-dependence was seen in N. norvegicus for most esterases, except AChE, with males displaying higher activities (p < 0.05). A sampling-depth effect was also seen in the crustacea, with animals from 100 m generally presenting lower esterase activities and higher LP levels.     

Mercury in Human Hair and Fish: is there a Hong Kong Male Subfertility Connection?

Hair is a useful indicator of a person’s exposure to mercury. For this reason, hair samples from 94 fertile and 117 subfertile Hong Kong residents were compared over four separate age groups. A typical 30 year old Hong Kong male had a hair mercury concentration of approximately 3.3 mg/kg mercury while a 60 year old Hong Kong subfertile male had a hair mercury concentration of about 7.5 mg/kg. Most of this mercury comes from seafood consumption. Individuals consuming four or more meals of fish per week had a hair mercury of 4.07 mg/kg dry weight of hair while those consuming fish less frequently had significantly lower levels (2.56 mg/kg). Hong Kong residents that consumed no fish had only 1.21 mg/kg hair mercury. The relative risks of males with moderate and high levels of mercury in their hair were significant (p=0.062). Age corrected estimates of risk indicated that compared with men with low levels of mercury in their hair, men with higher levels were twice as likely to be subfertile (relative risk, 1.95) and there was a dose–response trend that was highly significant (p < 0.0005). In light of these risks we concluded that the maximum permitted mercury level in food sold in Hong Kong should be lowered from 0.5 mg/kg wet weight to a level to be determined by risk analysis. In Japan, where fish mercury levels and fish consumption rates are lower than those in Hong Kong, the maximum amount of mercury permitted in food for human consumption is 0.3 mg/kg wet weight.     

Occurrence of estrogen-like substances in the marine environment of the Northern Mediterranean Sea

Evidence has been presented that a number of environmental agents perturbs the function of the sex hormone signalling pathways in marine animals.

In this work the estrogenic/antiestrogenic activity of coastal marine water samples from five sites of the Northern Mediterranean Sea was assayed using a recombinant Saccharomyces cerevisiae yeast strain (RMY326 ER-ERE) transfected with the human estrogen receptor . Extraction of potential EDCs from seawater was performed in columns packed with XAD-2 resins.

The estrogenic activity was calculated as percentage of the activity of 17β-estradiol (10 nM) and it ranged from 4.8% and 59.03%, significantly depending on sampling site (p = 0.0013) and season (p < 0.05). Antagonistic activity of extracts was also detected and the percentage of inhibition of estradiol-dependent β-galactosidase induction ranged to 52.8%. These results point the reliability of the yeast assay as a first level screening test to assess the quality of aquatic environments.     

Esterases activities and lipid peroxidation levels in muscle tissue of the shanny Lipophrys pholis along several sites from the Portuguese Coast

This study is part of a project aiming to validate the use of the intertidal shanny Lipophorys pholis as a sentinel species in pollution monitoring in NW European marine ecosystems. To this end, a characterisation of acethylcholin (AChE), butyrylcholin (BChE) and propionylcholin (PrChE) esterases in L. pholis muscle was performed and the results indicated that AChE was predominant. Furthermore, the use of eserine sulphate and BW284c51 (0.64–800 μM), and iso-OMPA (0.08–16 mM), confirmed the measurement of true cholinesterases (ChEs) as well as the presence of pseudocholinesterases. The field application of these markers to L. pholis, sampled in seven locations along the Portuguese coast, revealed that fish were likely to be affected by neurotoxic compounds. This was indicated by the significant depletion of AChE (p < 0.05) in animals collected at urban and industrialised sites, compared with those from reference locations. The inclusion of a marker of effect, measured as lipid peroxidation levels in muscle tissue, also revealed the existence of site differences. Overall, the study further validates the utility of L. pholis in pollution monitoring studies.     

Sulfate reduction using methane in sediments beneath a bathyal “cold seep” giant clam community off Hatsushima Island, Sagami Bay, Japan

Two sandy sediment cores (Cores D227-120 and D380) were collected from inside a deep-sea giant clam (Calyptogena soyoae) community off Hatsushima Island, western Sagami Bay, central Japan (35°59.9′N, 139°13.6′E; 1160 m deep) and a muddy sediment core (Core D227-202) was obtained from outside the community by the submersibleShinkai 2000. The chloride concentration of the pore waters is constant vertically and sulfate reduction using sedimentary organic matter occurs in Core D227-202 (21 cm long). The chloride concentrations are lower by 7% at the 7.5–9 cm depth in Core D227-120 (9 cm long) and by 3% at the 11–12 cm depth in Core D380 (16 cm long) than those of the overlying bottom waters in the cores from inside of the community. Sulfate concentration decreases remarkably and dissolved inorganic carbon, alkalinity, ammonium-N, and hydrogen sulfide concentrations increase significantly with increasing depth in Core D380.δ³⁴S values of sulfate ions increase from +20.5 to +35.3‰ andδ¹³C values of dissolved inorganic carbon decrease drastically from −7.0 to −45‰ with increasing depth from the top to the bottom of the core, although theδ¹³C values of the organic carbon of the sediments are−23.7 ± 0.9‰ in Core D380. These results indicate that sulfate reduction using methane is active within the sediments just beneath the living clams and that the hydrogen sulfide produced can be used by endosymbiotic sulfur oxidizing bacteria living in the gills ofC. soyoae in the community.     

Mercury,organic-mercury and selenium in small cetaceans in Taiwanese waters

Total Hg (∑Hg), organic-Hg (O-Hg) and Se bioaccumulations in small cetaceans distributed in Taiwanese waters of the Taiwan Strait and the southwestern Pacific have been investigated for the first time. The results could represent the baseline metal concentrations of marine mammals in the southwestern Pacific, where volcanic activities are possibly the major source of mercury to the environments. Muscle samples of four species of small cetaceans were collected from animals accidentally caught by tuna-longline fisheries from 1994 through 1995. In total, 53 pantropical spotted dolphins, Stenella attenuata, nine spinner dolphins, S. longirostris, five bottlenose dolphins, Turiops truncatus and four Risso's dolphins, Grampus giseus were analyzed. In addition, two stranded pantropical spotted dolphins were investigated. Cold vapour AAS and ICP-MS were used in the analysis of Hg and Se, respectively. Significant species difference was found in the four species of small cetaceans. Among them, the pantropical spotted dolphin showed the highest mean concentration (mg/kg wet wt.) of both ∑Hg (3.64±2.19) and O-Hg (2.79±1.23), whereas the Risso's dolphin had the highest mean concentrations of Se (1.77±1.29). There was no significant sex difference with respect to metal bioaccumulation in the samples of S. attenuata. Significant correlations between body length (BL) and ∑Hg, as well as O-Hg concentrations were observed in pantropical spotted (Sa) and spinner dolphins (Sl). The linear relationships were Sa: ∑Hg=−8.290+0.066BL, r=0.421; Sl: ∑Hg=−2.735+0.025BL, r=0.875; Sa: O-Hg=−3.723+0.036BL, r=0.408; and Sl: O-Hg=−3.017+0.025BL, r=0.870. However, a demethylation phenomenon that decreasing the percentage of O-Hg coupled with increasing levels of Se was observed when the ∑Hg concentrations in the muscle tissues of dolphins reached 4 mg/kg wet wt.     

Imposex in Morula Granulata as Bioindicator of Tributyltin (TBT) Contamination in the Dampier Archipelago, Western Australia

This study was undertaken to examine the use of imposex in the tropical neogastropod whelk Morula granulata as bioindicator of tributyltin (TBT) contamination. Samples were collected from sites throughout the Dampier Archipelago; both impact sites close to intensive shipping activity and remote control sites. TBT in this area originates mainly from commercial vessels using the Port of Dampier that are >25 m in length and exempt from legislation controlling the use of TBT in antifouling paints. A field survey was undertaken in July 1997; 100 M. granulata were taken at each of 18 sites with varying vessel activity, and examined for imposex. The level of TBT contamination in the Archipelago was low; ranging from <0.3 to 25 ng Sn l⁻¹ in water,<0.3 to 80 ng Sn g−¹ in oyster tissue (Saccostrea cuccullata – prey of M. granulata), and <0.3 to 33 ng Sn g⁻¹ in whelks. Percentage of imposex in M. granulata ranged from 0% to 57%, and was correlated with distance to vessel activity (r=0.646, p<0.05). The only significant relationship of imposex with butyltin concentrations was with TBT in oysters (r=0.826, p<0.05), and dibutyltin (DBT) in whelks (r=0.783, p<0.05). It is postulated that this is because of interspecies variation in ability to metabolize TBT to DBT and MBT (monobutyltin), as well as induction of imposex in earlier life stages, so that imposex in adults could be a reflection of prior contamination. M. granulata is a suitable bioindicator of TBT contamination in the Dampier Archipelago, which could be used throughout the Indo-Pacific given its abundance in the region.     

The Impact of the Herbicide Diuron on Photosynthesis in Three Species of Tropical Seagrass

The impact and recovery from exposure to the herbicide diuron [DCMU; 3-(3′,4′-dichlorophenyl)-1,1-dimethylurea] was assessed for three tropical seagrasses, maintained in outdoor aquaria over a 10-day period. Photosynthetic stress was detected using chlorophyll a fluorescence, measured with a Diving-PAM (pulse amplitude modulated fluorometer). Exposure to 10 and 100 μg l⁻¹ diuron resulted in a decline in effective quantum yield (ΔF/F_m^′) within 2 h of herbicide exposure in Cymodocea serrulata, Halophila ovalis and Zostera capricorni. Effective quantum yield also declined over the first 24 h of exposure in H. ovalis at even lower diuron concentrations (0.1 and 1.0 μg l⁻¹). Effective quantum yield in H. ovalis and Z. capricorni was significantly depressed at all diuron concentrations (0.1–100 μg l⁻¹) after 5 days exposure, whereas effective quantum yield in C. serrulata was only significantly lower in plants exposed to highest diuron concentrations (10 and 100 μg l⁻¹). Effective quantum yield depression was present 5 days after plants exposed to 10 and 100 μg l⁻¹ diuron were returned to fresh seawater. These results indicate that exposure to herbicide concentrations present in nearshore Queensland sediments present a potential risk to seagrass functioning.